본 연구에서는 분리막을 이용하여 천일염내 미세플라스틱을 비롯한 불순물을 제거하는 분리막 공정 설계를 위한 연구이다. 천일염 염전에 적합한 분리막 재질, 공경 사이즈, 모듈을 선정하여 다양한 조건에서 실험을 진행하였다. 선정된 200 kDa, 4 kDa 한외여과막 그리고 3 kDa 나노여과막을 선정하였고, 실험은 실험실과 실제 염전에 파일롯 플랜트를 건설하 여 각각 실험하였다. 천일염내 불순물은 대부분 0.1 μm 이상의 크기를 가졌고 크기 분포는 0.1 μm에서 1 μm 사이 입자가 가장 많은 부분을 차지하였다. 그리고 성분 분석결과 불순물 내에 7종류 이상의 다양한 미세플라스틱이 검출되었다. 분리막 공정 이후 여과된 염전수 분석한 결과 미세플라스틱을 포함한 불순물이 검출되지 않았고 기존의 천일염과 분리막 여과수로 제작한 천일염의 성분 비교해본 결과 천일염 성분의 변화 없이 불순물만 효과적으로 제거됨을 확인하였다.

Viscosity is a fundamental physical property that is important in any system in which fluid movement occurs. In addition, most of the elements exist as ions in molten state in high-temperature molten salt, and electrical conductivity in such molten state is closely related to viscosity as a transport property. Molten salt reactor (MSR) and pyroprocess are representative processes dealing with high-temperature molten salts, actinide elements, and other radioactive materials. In MSR and pyroprocesses, the viscosity data must be provided as one of the fundamental physical property data required for safe process operations and countermeasures to severe accidents. In order to measure the viscosity of highly corrosive molten salt at high temperatures, we have built a in-house developed molten salt viscosity measurement system based on the Brookfield rotationary viscometer. We also developed a special correction technique to improve the accuracy of the viscosity measurement. In this study, the viscosity was measured at 500°C for NaCl-MgCl2 molten salt, which is selected as the base salt material of MSR system under development in Korea Atomic Energy Research Institute (KAERI), using our viscosity measurement system installed in a oxygen- and moisture-free Ar-atmosphere glovebox. Our viscosity measurement system was calibrated using a LiCl-KCl eutectic mixture with well-known viscosity value, and viscosity values obtained using our own correction methodology were compared with those of other conventional correction methods. In our further study, we plan to measure the NaCl-MgCl2-UCl3 system at various compositions and temperatures.

Molten salt reactor (MSR) is one of the non-pressurized-water fourth-generation reactors that uses liquid nuclear fuel that integrates coolant and nuclear fuel, so it is a safe reactor that can fundamentally prevent severe accidents caused by coolant loss. MSR uses NaCl-MgCl2 as a coolant salt, which is considered a promising diluent that can dissolve the fuel salt by forming an eutectic mixture. In this study, a zone-melting system was used to remove impurities from the NaCl-MgCl2 used in MSR. The system was designed in detail to control eutectic salt impurities by traversing long charges into a small molten zone.

In this study, molten salt experiments were performed using a multi-purpose molten salt experimental loop to evaluate the corrosion and thermodynamic properties of the molten salt. The multi-purpose molten salt experimental loop is made of 1-inch austenitic 316 stainless steel, and 1/4-inch austenitic 316 stainless steel tubes were welded on the surface of a 1-inch pipe to measure temperatures of molten salt. During the experiment, the molten salt leaked due to corrosion of the welded part of the 1/4-inch tube connected to the 1-inch pipe. Therefore, the cause of corrosion damage of the leaked welded part was analyzed. The effect of NaCl-MgCl2 salt selected as the molten salt on corrosion failure was considered. And based on the operation data of molten salt experiments, the time of occurrence of the issue was estimated. Lastly, the cause of corrosion failure was estimated by comparing and analyzing the pipe shape before and after failure using SEM-EDS.

Molten chloride salts are promising candidates as a coolant for Molten Salt Reactors (MSRs) because of their low cost, high specific heat transfer, and thermal energy storage capacity. The NaCl- MgCl2 eutectic salts have enormous latent heat (430 kJ/kg) and financial advantage over other types of molten chloride salt. Despite the promise of the NaCl-MgCl2 eutectic salt, problems associated with structural material corrosion in the MSR system remain. The hygroscopicity of NaCl-MgCl2 and high MSRs operating temperature accelerate corrosion within structural alloys. Especially, MgCl2 reacts with H2O in the eutectic salt to produce HCl and Cl2, which are known to further exacerbate corrosion by the chlorination of structural materials. Therefore, several studies have worked to purify impurities associated with MgCl2, such as H2O. Thermal salt purification of NaCl-MgCl2 eutectic salt is one method that reduces HCl and Cl2 gas generation. However, MgO and MgOHCl are generated as the byproduct of thermal purification through a reaction between MgCl2 and H2O. The corrosion behavior of MgO within structural alloys after thermal treatment is not well known. This paper demonstrates corrosion behavior within structural alloy after thermal treatment at various temperature profiles of the NaCl-MgCl2 eutectic salt. According to the temperature range, MgCl2·H2O are separated at 100~200°C, and MgOHCl and HCl begin to occur at 240°C or higher. Finally, MgOHCl produces MgO and HCl at 500°C or higher temperatures. After thermal treatments, the H2O, MgOHCl, and MgO content were measured by Thermo Gravimetric Analyzer (TGA) to evaluate significant products causing corrosion. The structural materials were analyzed by the Scanning Electron Microscope-Energy Dispersive Spectroscopy (SEM-EDS) and using the mass change method to observe the type of localized corrosion, the corrosion rate, and the corrosion layer thickness. This study is possible in that it can reduce economic costs by reducing the essential use of expensive, high-purity molten salts because it is related to a substantial financial cost problem considering the amount of molten salt used in industrial sites.

Plasma Arc Melter (MSO) system has been developed for the treatment and the stabilization of various kinds of hazardous and radioactive waste into the readily disposable solidification products. Molten salt oxidation system has been developed for the for the treatment of halogen- and sulfurbearing hazardous and radioactive waste without emissions of PCDD/Fs and acid gases. However, PAM system has showed some difficulty in the off-gas treatment system due to the volatilization of radionuclides and toxic metals at extremely high-temperature plasma arc melter and the emissions of acid gases. MSO system has also showed the difficulty in the treatment of spent molten salt into the disposable waste form. Present study discussed the results of organics destruction performance tests for the PAM-MSO combination system, which is proposed and developed to compensate the drawbacks of each system. The worst-case condition tests for the organics destruction were conducted at lowest temperatures and the worst-case condition tests for the retention of metals and radionuclides were conducted at highested temperatures under the range of normal operating condition. For the worst-case organic destruction test, C6H5Cl was selected as a POHCs (Principal Organic Hazardous Constituents) because of its high incinerability ranking and the property of generation of chlorine gases and PCDD/Fs when incompletely destroyed. Simulated concrete waste spiked with 1 L of C6H5Cl was treated and the emissions of 17 kinds of PCDD/Fs and other hazardous gases such as CO, THCs, NOx, SO2 and HCl/Cl2 were measured. For the worst-case condition tests for the retention of metals and radionuclides, Pb and Cs were selected because of its high volatility characteristics. The emissions of PCDD/Fs was extremely lowered than the emission limit and those of other hazardous constituents were below their emission limit. The results of performance tests on the organics destruction suggested that tested PAM-MSO combination system could readily treat PCBs-bearing spent insulation liquid, spent ion-exchange resins used for the treatment of spent decontamination liquid in the decommission process and the concreted debris bearing hazardous organic coating materials. The decontamination factor of Cs and Co were 1.4×105, 1.4×105, respectively. The emisison of Pb was 0.562 ppm. These results suggested that tested PAM-MSO system treated low-level radioactive and pb-bearing mixed waste.

Present study investigated the waste form integrity of melted products generated from PAM-MSO system, which is proposed and developed to compensate the drawbacks of each system. The disposal suitability of the melting solidification products generated from the plasma arc melting treatment of pulverized cement debris spiked by Pb, Cd and Cs, as indicators of typical hazardous metals and radionuclides existed in the low-level mixed waste in the KHNPPs. The final waste form obtained by the test was evaluated for suitability for disposal. The compressive strength was 261.10 MPa, showing much higher values when compared to other waste form products. The compressive strength of both the sample after irradiation with 107 Gy radiation and that after long-term submersion test (90 days) satisfied the disposal criteria. As a result of the leaching test conducted according to the ANS 16.1 test method, it was confirmed that the leaching index satisfies the disposal criteria.

Molten Salt Reactor, which employs molten salt mixture as fuel, has many advantages in reactor size and operation compared to conventional nuclear reactor. In developing Molten Salt Reactor, Offgas system should be properly designed since the fission products in off-gas accelerates the corrosion in reactor structure materials and deteriorates the purity of liquid fuel. The design of off-gas system therefore requires the preliminary study of the behavior of evolved fission products in off-gas units and the development of off-gas model is crucial in developing such system. In this study, we corrected the off-gas illustrative model proposed by ORNL (Nuclear Engineering and Design, vol 385(15) 111529, 2021) by employing physically consistent concept of capture rate of fission product and holdup. For the application of the corrected off-gas model to Chloride-based 6 MW Molten Salt Reactor, major fission products were firstly determined from OpenMC based neutronics calculation and chain reaction related to the major fission products were defined. Based on these data, the holdup behavior of fission products in off-gas units (decay tank, caustic scrubber, Halide trap, H2O trap and charcoal bad) were investigated.

Based on the results of a review for various precipitation methods phosphorylation (phosphate precipitation) of metal chlorides considered as a proper treatment method for recovering of the fission products in a molten salt. In previous precipitation tests, the powder of lithium phosphate (Li3PO4) added into LiCl-KCl molten salt containing metal chlorides as a precipitation agent. The reaction of metal chlorides containing actinides and rare earths to recover with lithium phosphate in a molten salt known as solid-liquid reaction. The powder of lithium phosphate disperse in a molten salt by stirring thoroughly in order to enhance the precipitation reaction. As a result, metal phosphates as the reaction products precipitate on the bottom of the vessel and cutting at the lower part of the salt ingot considered as one of the recovery method of the precipitates. Recently, the vacuum distillation of upper part of the salt proposed as another recovering method. Cutting method of precipitate at the lower part of the salt ingot would be difficult to handle the increased size of the salt ingot produced from the practical scale equipment. In this presentation, a new method for collecting the precipitates of phosphorylation reaction into a small vessel is introduced with test results in a molten salt containing uranium and rare earths such as Nd, Ce, and La. As the first step of a series of test lithium phosphate ingot was prepared by melting the powder at a temperature 1,300°C, and the ingot put into LiCl-KCl molten salt at 500°C for more than three hours to examine the shape of ingot to be deformed or not. The phosphorylation experiments using lithium phosphate ingots carried out to collect the metal phosphate precipitates and the test result of this new method was feasible.

Under the circumstance of energy transition policy of the previous government in which nuclear energy portion will be gradually reduced, some R&D study looking for alternatives other than Pyro- SFR recycling could be very valuable and timely suitable. New alternative study started to evaluate the possibility of it if there are some advantages in terms of waste burden in case that the spent fuel are appropriately treated and disposed of in a disposal site, instead of recycling of spent nuclear fuels (SNF). The alternative study separate the fission products (minor actinides and rare earths) from SNF in a molten salt medium. The molten salt coming from the alternative study is radioactive and heat generating because it contains the fission products chlorides. It is necessary to collect the fission products from the waste molten salt for minimization of the high-level waste volume and to generate a final waste form containing the fission products compatible to the disposal site. Based on the results of a review for various precipitation methods, phosphorylation (phosphate precipitation) of metal chlorides selected as a proper treatment method for recovering of the fission products in a molten salt. Phosphate precipitation has the potential for removing most of fission product elements from a molten salt arising from the treatment of spent nuclear fuel. The performance of phosphate precipitation method evaluated using a salt mixture with the actinide and rare earth chlorides. The molten salt containing uranium as surrogate of the actinides and three rare earths (Nd, Ce, La) chloride was used for testing a phosphate precipitation method at experimental condition (temperature 500°C, salt stirring 200~300 rpm, and 1~1.2 eq. of phosphorylation agent). A cyclic voltammetry (CV) method monitored in-situ phosphate precipitation progress for determining the precipitation rate and conversion ratio evaluated. The phosphorylation reaction increased greatly at a salt stirring 300 rpm.

During electrorefining, fission products, such as Sr and Cs, accumulate in a eutectic LiCl-KCl molten salt and degrade the efficiency of the separation process by generating high heat and decreasing uranium capture. Thus, the removal of the fission products from the molten salt bath is essential for reusing the bath, thereby reducing the additional nuclear waste. While many studies focus on techniques for selective separation of fission products, there are few studies on processing monitoring of those techniques. In-situ monitoring can be used to evaluate separation techniques and determine the integrity of the bath. In this study, laser-induced breakdown spectroscopy (LIBS) was selected as the monitoring technique to measure concentrations of Sr and Cs in 550°C LiCl-KCl molten salt. A laser spectroscopic setup for analyzing high-temperature molten salts in an inert atmosphere was established by coupling an optical path with a glove box. An air blower was installed between the sample and lenses to avoid liquid splashes on surrounding optical products caused by laser-liquid interaction. Before LIBS measurements, experimental parameters such as laser pulse energy, delay time, and gate width were optimized for each element to get the highest signal-to-noise ratio of characteristic elemental peaks. LIBS spectra were recorded with the optimized conditions from LiCl-KCl samples, including individual elements in a wide concentration range. Then, the limit of detections (LODs) for Sr and Cs were calculated using calibration curves, which have high linearity with low errors. In addition to the univariate analysis, partial least-squares regression (PLSR) was employed on the data plots to obtain calibration models for better quantitative analysis. The developed models show high performances with the regression coefficient R2 close to one and root-mean-square error close to zero. After the individual element analysis, the same process was performed on samples where Sr and Cs were dissolved in molten salt simultaneously. The results also show low-ppm LODs and an excellent fitted regression model. This study illustrates the feasibility of applying LIBS to process monitoring in pyroprocessing to minimize nuclear waste. Furthermore, this high-sensitive spectroscopic system is expected to be used for coolant monitoring in advanced reactors such as molten salt reactors.

It has been studied on the disposal area reduction for the used nuclear fuel by the management of high decay-heat nuclides, long-lived nuclides, and highly mobile nuclides. It was investigated on the management of the nuclides in KAERI. Strontium-90 is a high heat-generating nuclide in spent nuclear fuel. It is needed to separate the salt from the salt solution for the recovery of strontium after the chlorination of the strontium oxide in molten salt. Vacuum distillation was used for the separation of strontium from the molten salt. Potassium carbonate was chosen as a reactive distillation reagent for SrCl2 – LiCl – KCl system by the thermodynamic calculation. Reactive distillation experiments were carried out. The residual was mainly SrCO3 in the XRD analysis. It could be concluded that K2CO3 could be one of the suitable reagents for the reactive distillation. The salt in the long–lived nuclide powders should be removed to prepare the block for disposal. Experiments were carried out using W powders (surrogate) and U3O8 powders to develop a process for the removal of the residual salt from UOx powders. The salts were successfully removed from the W and U3O8 powders by distillation.

The effect of Li2O addition on precipitation behavior of uranium in LiCl-KCl-UCl3 has been investigated in this study. 99.99% LiCl-KCl eutectic salt is mixed with 10wt% UCl3 chips at 550°C in the Pyrex tube in argon atmosphere glove box, with 10 ppm O2 and 1 ppm H2O. Then, Li2O chunks are added in mixed LiCl-KCl-UCl3 and the system has been cooled down to room temperature for 10 hours to form enough UO2 particles in the salt. The solid salt has been taken out from the glove box, and cut into three sections (top, middle and bottom) by low-speed saw for further microscopic analysis. Three pieces of solid salt are dissolved in deionized water at room temperature and the solution is filtered by a filter paper to collect non-dissolved particles. The filter paper with particles is baked in vacuum oven at 120°C for 6 hours to evaporate remaining moisture from the filter paper. Further analysis was performed for the powder remaining on the filter paper, and periphery of the powder (cake) on the filter paper. Scanning electron microscopy (SEM), electron diffraction spectroscopy (EDS), and X-ray powder diffraction (XRD) are adopted to analysis the characteristic of the particles. From SEM analysis, the powders are consisted of small particles which have 5 to 10 m diameter, and EDS analysis shows they are likely UO2 with 23 at. % of uranium and 77 at. % oxygen. Cake is also analyzed by SEM and EDS, and needle like structures are widely observed on the particle. The length of needle is distributed from 5 to 20 m, and it has 6 to 10 at. % of chlorine, which are not fully dissolved into deionized water at room temperature. From XRD analysis, the particles show the peak position of UO2, and the result is well matched with the SEM-EDS results. We are planning to add more Li2O in the system for fully reacting uranium in UCl3, and compare the results to find the effect of Li2O concentration on UO2 precipitation.

One of the promising candidates for heat transfer fluid is molten chloride salts. They have been studied in various fields such as the electrolyte of pyroprocessing, the molten salt reactor coolant, and the energy storage system media. Main considerations for utilizing molten chloride salts are the compatibility of salts with structural materials. The corrosion behavior of structural materials in molten chloride salts must be understood to identify suitable materials against the corrosive environment. In this study, the corrosion behavior of a candidate structural material, Hastelloy N, in molten LiCl- KCl salt at 500°C were investigated by the electrochemical impedance spectroscopy (EIS) method. The sheet type of Hastelloy N was utilized as the working electrode in LiCl-KCl to measure the EIS data for 100 hours with 5 hours of time intervals. The EIS data were measured in the frequency range from 104 Hz to 10-2 Hz with the AC signal (amplitude = 20 mV) at open circuit potential. The capacitance semicircle observed in Nyquist plots for all periods indicates that charge-transfer controlled reactions occur. As the immersion time progresses, the radius of the semicircle in Nyquist plots and the impedance and phase angle in Bode plots decrease. These behaviors suggest a decreasing reaction resistance and the corrosion reactions are accelerated with the immersion time. The EIS data were fitted using the equivalent circuit to achieve quantitative results. Two capacitor-resistor components were considered due to the overlapped shape of two valleys in phase angle. The depressed shape of the semicircle in Nyquist plots led to the use of the constant phase element(Q) instead of the capacitor. Therefore, R(Q(R(QR))) circuit was selected to fit the EIS data. Fitting results show that the charge transfer resistance decreases dramatically within 1 day and then converges. The film resistance shows no clear trends, but the increase of the film admittance value indicates the decreased film thickness. Consequently, the film appears to exist like the oxide layer but it does not act as a protective layer. The real-time EIS data were measured in molten salt and provides the corrosion behavior over time. The corrosion mitigation strategy should consider that the corrosion of Hastelloy N accelerates over time and its intrinsic film cannot act as the protective layer. The next steps of this study are to evaluate other candidate structural materials and to demonstrate the presence of the film.

PURPOSES : Snow removal is one of the principal components in winter road maintenance. The two commonly used methods are mechanical removal and chemical removal. Mechanical removal pushes accumulated snow off the roadway using snow plows. Chemical removal involves the application of chemicals such as NaCl2 (salt), CaCl2, MgCl2, etc., to liquefy the snow on the road. However, chemicals are known to pose negative effects on the environment and road infrastructure, so it is emphasized that only an appropriate amount of chemicals should be applied. Hence, in this study, extensive field experiments were performed to determine the appropriate amounts of chemicals required for each road surface temperature group. METHODS : The experiments were carried out at a road weather proving ground, located in Yeoncheon where road weather (including snowfall) can be artificially created. Four surface temperature groups were predetermined, according to the characteristics of de-icing chemicals on snow. For each temperature group, four different amounts of pre-wetted salt were applied to find the optimal rate for each group. RESULTS : As a consequence, the amount of recommended chemicals for each temperature group was found to be an average of 27.2g/ m2, which is 7.7g/m2 (22%) lower than the corresponding amount presented in the current Korean guidelines. CONCLUSIONS : Applying the results of this study to snow and ice control tasks enables the minimization of the negative impacts of de-icing chemicals, but still maintaining road safety and mobility.

Molten salt consisting primarily of eutectic LiCl-KCl is currently being used in electrorefiners in the Fuel Conditioning Facility at Idaho National Laboratory. Options are currently being evaluated for storing this salt outside of the argon atmosphere hot cell. The hygroscopic nature of eutectic LiCl-KCl makes is susceptible to deliquescence in air followed by extreme corrosion of metallic cannisters. In this study, the effect of occluding the salt into a zeolite on water sorption/desorption was tested. Two zeolites were investigated: Na-Y and zeolite 4A. Na-Y was ineffective at occluding a high percentage of the salt at either 10 or 20wt% loading. Zeolite-4A was effective at occluding the salt with high efficiency at both loading levels. Weight gain in salt occluded zeolite-4A (SOZ) from water sorption at 20% relative humidity and 40℃ was 17wt% for 10% SOZ and 10wt% for 20% SOZ. In both cases, neither deliquescence nor corrosion occurred over a period of 31 days. After hydration, most of the water could be driven off by heating the hydrated salt occluded zeolite to 530℃. However, some HCl forms during dehydration due to salt hydrolysis. Over a wide range of temperatures (320–700℃) and ramp rates (5, 10, and 20℃ min−1), HCl formation was no more than 0.6% of the Cl− in the original salt.

This work provided a review of three techniques—(1) spectrochemical, (2) electrochemical, and (3) spectroelectrochemical– for molten salt medias. A spectroelectrochemical system was designed by utilizing this information. Here, we designed a spectroelectrochemical cell (SEC) and calibrated temperature controllers, and performed initial tests to explore the system’s capability limit. There were several issues and a redesign of the cell was accomplished. The modification of the design allowed us to assemble, align the system with the light sources, and successfully transferred the setup inside a controlled environment. A preliminary run was executed to obtain transmission and absorption background of NaCl-CaCl2 salt at 600°C. It shows that the quartz cuvette has high transmittance effects across all wavelengths and there were lower transmittance effects at the lower wavelength in the molten salt media. Despite a successful initial run, the quartz vessel was mated to the inner cavity of the SEC body. Moreover, there was shearing in the patch cord which resulted in damage to the fiber optic cable, deterioration of the SEC, corrosion in the connection of the cell body, and fiber optic damage. The next generation of the SEC should attach a high temperature fiber optic patch cords without introducing internal mechanical stress to the patch cord body. In addition, MACOR should be used as the cell body materials to prevent corrosion of the surface and avoid the mating issue and a use of an adapter from a manufacturer that combines the free beam to a fiber optic cable should be incorporated in the future design.

Electroanalytical study for the rotating cylinder electrode in molten LiCl-KCl eutectic salt (58– 42mol%) containing MgCl2 (0.1wt%) at 600°C is conducted. The researches of rotating cylinder electrode have been widely conducted for the century. The advantage of the electrode is that it can mitigate the unintended natural convection by providing a controlled diffusion boundary layer thickness. However, the experimental data for the high temperature molten salts is barely existed. The study adopts the electrochemical techniques such as cyclic voltammetry for the static cell and linear sweep voltammetry for the dynamic cell to calculate the diffusion coefficient. The peak current density and limiting current density are measured according to the scan rate. In order to evaluate the mass transfer under hydrodynamic flow condition, the revolution speeds of cylindrical electrode are varied from 10 rpm to 500 rpm which are corresponded to the Reynolds number of 4 and 185 respectively. The flow regime covers from the laminar to semi-turbulent regime (transient) as the critical Reynolds number Recrit is 200. The limiting current density shows a linear trend with the revolution speed and agrees well with the existing mass transfer correlations. For the extended flow regime, a new mass transfer correlation is suggested as the relation of non-dimensional numbers (Sh = aRebScc) based on the dimensionless analysis.

At high temperatures, molten salt has heat transfer properties like water. Molten salt has the characteristics of a strong natural circulation tendency, large heat capacity, and low thermal conductivity. Unlike sodium, molten salt does not react explosively exothermically with air. However, molten salt has a strong tendency to corrode materials, and its properties are easily changed by a sensitive reaction to oxygen and moisture. Therefore, it is necessary to study material corrosion properties and chemical control methods for nuclear fuel salts, which are eutectic mixtures. In this study, the optimal operation method of the thermal convection loop is established to perform the experiments on the molten salt. The process describes briefly as follows. The operation step consists of preparation, purification, transportation, and operation. In the preparation, the step checks the entire structure and equipment (TC, blower, vacuum pump, etc.). And melt the salt mixture at a high temperature (670°C) slowly in the purification step. Before injecting the molten salt, the surface temperature of the entire loop must retain temperature (about 500°C) constantly. Completely melted molten salt in the melting pot is flow along the pipe of the thermal convection loop in the transportation step. Lastly, the convection of molten salt goes to keep by the temperature difference. The thermal convection loop can be utilized for various experiments such as corrosion tests, component analyses, chemistry control, etc.